Selective Deposition Of Thin Film Dielectrics Using Surface Blocking Chemistry

ABSTRACT

Methods of depositing a film selectively onto a first substrate surface relative to a second substrate surface. Methods include soaking a substrate surface comprising hydroxyl-terminations with a silylamine to form silyl ether-terminations and depositing a film onto a surface other than the silyl ether-terminated surface.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application No.62/155,529, filed May 1, 2015, the entire disclosure of which is herebyincorporated by reference herein.

FIELD

Embodiments of the disclosure generally relate to methods of selectivelydepositing a film. More particularly, embodiments of the disclosure aredirected to methods of selectively depositing a film using alcoholselective reduction and selective protection.

BACKGROUND

Selective deposition processes are gaining a lot of momentum mostlybecause of the need for patterning applications for semiconductors.Traditionally, patterning in the microelectronics industry has beenaccomplished using various lithography and etch processes. However,since lithography is becoming exponentially complex and expensive theuse of selective deposition to deposit features is becoming much moreattractive. Another potential application for selective deposition isgap fill. In gap fill, the fill film is grown selectively from thebottom of a trench towards the top. Selective deposition could be usedfor other applications such as selective sidewall deposition where filmsare grown on the side of the fin. This would enable the deposition of asidewall spacer without the need for complex patterning steps.

Therefore, there is a need in the art for methods of selectivelydepositing a film onto one surface selectively over a different surface.

SUMMARY

One or more embodiments of the disclosure are directed to methods ofdepositing a film. A substrate comprising a first substrate surfaceincluding hydroxyl-terminated surface and a second substrate surfaceincluding a hydrogen-terminated surface is provided. The substrate isexposed to a silylamide to react with the hydroxyl-terminated surface toform a silyl ether-terminated surface. The substrate is exposed to oneor more deposition gases to deposit a film on second substrate surfaceselectively over the silyl ether-terminated surface.

Additional embodiments of the disclosure are directed to methods ofdepositing a film. A substrate comprising a first substrate surfaceincluding a hydroxyl-terminated surface and a second substrate surfaceincluding a hydrogen-terminated dielectric is provided. The substrate issoaked with a silylamide to react with the hydroxyl-terminated surfaceto form a silyl ether-terminated surface. The substrate is exposed toone or more deposition gases to deposit a silicon nitride film on thesecond substrate surface selectively over the first substrate surface.

Further embodiments of the disclosure are directed to methods ofdepositing a film. A substrate comprising a first substrate surfaceincluding a hydroxyl-terminated surface and a second substrate surfaceincluding a hydrogen-terminated dielectric is provided. The substrate issoaked with a silylamide comprising one or more of1-trimethylsilylpyrrolidine, 1-trimethylsilylpyrrole and/or3,5-dimethyl-1-trimethylsilylpyrazole to react with thehydroxyl-terminated surface to form a silyl ether-terminated surface.The substrate is exposed to one or more deposition gases to deposit asilicon nitride film on the second substrate surface selectively overthe first substrate surface.

BRIEF DESCRIPTION OF THE DRAWINGS

So that the manner in which the above recited features of the presentdisclosure can be understood in detail, a more particular description ofthe disclosure, briefly summarized above, may be had by reference toembodiments, some of which are illustrated in the appended drawings. Itis to be noted, however, that the appended drawings illustrate onlytypical embodiments of this disclosure and are therefore not to beconsidered limiting of its scope, for the disclosure may admit to otherequally effective embodiments.

FIG. 1 shows a schematic representation of a processing method inaccordance with one or more embodiment of the disclosure; and

FIG. 2 shows an embodiment of a batch processing chamber in accordancewith one or more embodiment of the disclosure.

DETAILED DESCRIPTION

There are a variety of methods that could be used for selectivedepositions. Embodiments of the disclosure are directed to methods thatemploy surface deactivation by taking advantage of the surface chemistryof two different surfaces. Since two different surfaces will havedifferent reactive handles, the differences can be taken advantage of byutilizing molecules that will react with one surface (to deactivate thatsurface) and not react with the other surface. Some embodiments of thedisclosure use trimethylsilylamide chemistry to react with Si—OH groupsof one surface and not react with Si—H terminated second surface.

As used in this specification and the appended claims, the term“substrate” and “wafer” are used interchangeably, both referring to asurface, or portion of a surface, upon which a process acts. It willalso be understood by those skilled in the art that reference to asubstrate can also refer to only a portion of the substrate, unless thecontext clearly indicates otherwise. Additionally, reference todepositing on a substrate can mean both a bare substrate and a substratewith one or more films or features deposited or formed thereon.

A “substrate” as used herein, refers to any substrate or materialsurface formed on a substrate upon which film processing is performedduring a fabrication process. For example, a substrate surface on whichprocessing can be performed include materials such as silicon, siliconoxide, strained silicon, silicon on insulator (SOI), carbon dopedsilicon oxides, silicon nitride, doped silicon, germanium, galliumarsenide, glass, sapphire, and any other materials such as metals, metalnitrides, metal alloys, and other conductive materials, depending on theapplication. Substrates include, without limitation, semiconductorwafers. Substrates may be exposed to a pretreatment process to polish,etch, reduce, oxidize, hydroxylate, anneal and/or bake the substratesurface. In addition to film processing directly on the surface of thesubstrate itself, in the present disclosure, any of the film processingsteps disclosed may also be performed on an underlayer formed on thesubstrate as disclosed in more detail below, and the term “substratesurface” is intended to include such underlayer as the contextindicates. Thus for example, where a film/layer or partial film/layerhas been deposited onto a substrate surface, the exposed surface of thenewly deposited film/layer becomes the substrate surface. What a givensubstrate surface comprises will depend on what films are to bedeposited, as well as the particular chemistry used. In one or moreembodiments, the first substrate surface will comprise a metal, and thesecond substrate surface will comprise a dielectric, or vice versa. Insome embodiments, a substrate surface may comprise certain functionality(e.g., —OH, —NH, etc.).

Likewise, the films that can be used in the methods described herein arequite varied. In some embodiments, the films may comprise, or consistessentially of a metal. Examples of metal films include, but are notlimited to, cobalt (Co), copper (Cu), nickel (Ni), tungsten (W), etc. Insome embodiments, the film comprises a dielectric. Examples include,SiO₂, SiN, HfO₂, etc.

As used in this specification and the appended claims, the terms“reactive gas”, “precursor”, “reactant”, and the like, are usedinterchangeably to mean a gas that includes a species which is reactivewith a substrate surface. For example, a first “reactive gas” may simplyadsorb onto the surface of a substrate and be available for furtherchemical reaction with a second reactive gas.

Embodiments of the disclosure provide methods of selectively depositinga metal film onto one surface over a second surface. As used in thisspecification and the appended claims, the term “selectively depositinga film on one surface over another surface”, and the like, means that afirst amount of the film is deposited on the first surface and a secondamount of film is deposited on the second surface, where the secondamount of film is less than the first amount of film or none. The term“over” used in this regard does not imply a physical orientation of onesurface on top of another surface, rather a relationship of thethermodynamic or kinetic properties of the chemical reaction with onesurface relative to the other surface. For example, selectivelydepositing a cobalt film onto a copper surface over a dielectric surfacemeans that the cobalt film deposits on the copper surface and less or nocobalt film deposits on the dielectric surface; or that the formation ofthe cobalt film on the copper surface is thermodynamically orkinetically favorable relative to the formation of a cobalt film on thedielectric surface.

With reference to FIG. 1, one or more embodiments of the disclosure aredirected to methods of depositing a film. A substrate 10 comprising afirst substrate surface 12 and a second substrate surface 14 isprovided. The first substrate surface 12 includes a hydroxyl-terminatedsurface (i.e., a surface having —OH groups). The second substratesurface 14 includes a hydrogen-terminated surface (i.e., a surfacehaving —H terminations, e.g., Si—H or Si—NH₂). A hydrogen-terminatedsurface can include an amine terminated surface (as might be found in aSiN film). In some embodiments, the first substrate surface 12 comprisessubstantially only hydroxyl-terminations. As used in this regard, theterm “substantially only” means that the surface terminations of thefirst substrate surface are at least about 75%, 80%, 85%, 90% or 95%hydroxyl terminations. In some embodiments, the second substrate surface14 comprises substantially only hydrogen terminations. As used in thisregard, the term “substantially only” means that the surfaceterminations of the second substrate surface are at least about 75%,80%, 85%, 90% or 95% hydrogen terminations. In some embodiments, one ormore of the first substrate surface 12 and the second substrate surface14 comprises a dielectric. In one or more embodiments, the firstsubstrate surface 12 comprises a dielectric. The dielectric can be alow-k dielectric or a high-k dielectric.

The substrate 10 is exposed to a silylamide to react with one or more ofthe first substrate surface 12 and/or the second substrate surface 14.Exposing the substrate surface to the silylamide can be done by anysuitable process. Exposure may be referred to as soaking, in which atleast some of the substrate surfaces are “soaked” or “flooded” with thesilylamide to allow surface reactions to occur. As used in thisspecification and the appended claims, the term “silylamide” refers to acompound have a silicon-nitrogen bond in which the nitrogen is part ofan amine group or part of a heterocyclic ring. FIG. 1 shows a schematicof the initial surface reactions that occur on a Si—OH terminatedsurface (the first substrate surface 12) versus a Si—H terminatedsurface (the second substrate surface 14).

Silicon-carbon bonds are very strong and not very reactive. Withoutbeing bound by any particular theory of operation, it is believed that asilylamide can deactivate any surfaces by the silicon-carbon bond.Silicon-carbon bonds are also thermally stable, showing stability up to600° C. Silylamide groups are not reactive towards the basic Si—H groupand will not deactivate surfaces terminated with Si—H. It has been foundthat use of a silylamide can allow for selectively depositing certaindielectric processes on Si—H and not on Si—OH terminated surfaces.

The silylamide in FIG. 1 is denoted by (CH₃)₃Si-L in which L is anyamine or heterocyclic amine. The silylamide shown in FIG. 1 is merelyindicative of one possible silylamide and should not be taken aslimiting the scope of the disclosure. The silylamide reacts with thehydroxyl-terminations on the first substrate surface 12 to form a silylether-terminated surface 13 and evolve HL. As used in this specificationand the appended claims, the term “silyl ether” refers to a compoundhaving a Si—O bond that forms a surface termination.

Suitable silyamides are those that can react with the surface hydroxylgroups to form a silyl ether terminated surface. In some embodiments,the silylamide comprises an organic silylamide. As used in thisspecification and the appended claims, the term “organic silylamide”refers to a compound in which the silicon atom is bonded to one or moreorganic groups. For example, as shown in FIG. 1, the organic silylamideis a trimethylsilyl amide.

In one or more embodiments, the organic silylamide comprises a siliconatom bonded substantially only to carbon and/or nitrogen atoms. As usedin this specification and the appended claims, the term “substantiallyonly to carbon and/or nitrogen” means that there is less than about 5%of the silicon atoms are bonded to atoms other than carbon or nitrogen,on an atomic basis. In one or more embodiments, the organic silylamidecomprises substantially no Si—H or Si—OH bonds. As used in thisspecification and the appended claims, the term “substantially no Si—Hand/or Si—OH bonds” means that there is less than about 5% of thesilicon atoms are bonded to hydrogen or hydroxides.

In some embodiments, the organic silylamide comprises one or more oftrimethylsilylamide, triethylsilylamide, ethyldimethylsilylamide and/ordiethylmethylsilylamide. In one or more embodiments, the silylamideincludes an amide comprising one or more of pyrrolidine, pyrrole,pyrazole, dimethylamine, diethylamine, ethylmethylamine, cyclicsecondary amine, saturated cyclic amine and/or unsaturated cyclic amine.

Trimethylsilylamides contain a basic amine group which will readilyreact with Si—OH groups to form the free amine and result in theformation of a very stable (CH3)3Si—O—Si moiety. In certain embodiments,the silylamide comprises one or more of 1-trimethylsilylpyrrolidine,1-trimethylsilylpyrrole and/or 3, 5-dimethyl-1-trimethylsilylpyrazole.

The temperature at which the pre-treatment (i.e., the silylamide) isexposed to the substrate surfaces depends on, for example, the firstsurface, the second surface, the silylamide, planned future processing,past processing and the processing equipment being used. For example, alower temperature process may help preserve the thermal budget of thesubstrate for further processing. In some embodiments, the substratesurfaces are exposed to the silylamide at a temperature in the range ofabout 50° C. to about 600° C.

The silylamide exposure time can vary depending on, for example, thereactivity of the silylamide toward the subject surface materials. Insome embodiments, the substrate is exposed to the silylamide for a timein the range of about 10 seconds to about 60 minutes. In someembodiments, the silylamide exposure occurs for a time less than about10 minutes, 5 minutes, 1 minute or 0.5 minutes.

After formation of the silyl-ether terminated surface 13, a film can bedeposited onto the second substrate surface 14 without affecting thesilyl-ether terminated surface 13. The film can be deposited by anysuitable technique. In some embodiments, the substrate 10 is exposed toone or more deposition gases to deposit a film 15 on the secondsubstrate surface 14 selectively versus the silyl-ether terminatedsurface 13. In one or more embodiments, the deposited film 15 comprisesSiN. The film 15 of some embodiments is deposited by atomic layerdeposition comprising sequential exposure to a silicon-containing gasand a nitrogen-containing gas. Suitable silicon-containing gasesinclude, but are not limited to silane, disilane, trisilane,monochlorosilane, dichlorosilane, trichlorosilane, silicontetrachloride, hexachlorodisilane (HCDS), a halogenated carbosilane andcombinations thereof. Suitable nitrogen-containing gases include, butare not limited to, nitrogen-containing plasma, ammonia, an amine,hydrazine and/or carbonitride.

The film formation process can be CVD process in which the firstreactive gas and the second reactive gas are exposed to the substratesurface at the same time so that the first reactive gas and the secondreactive gas mix during formation of the film.

In some embodiments, the film formation process is an ALD process inwhich the substrate, or portion of the substrate, is sequentiallyexposed to the first reactive gas and the second reactive gas.Sequential exposure means that the substrate, or portion of thesubstrate, is exposed to only one of the first reactive gas and thesecond reactive gas at any given time. In ALD processes there issubstantially no gas phase mixing of the first reactive gas and thesecond reactive gas.

FIG. 2 shows an embodiment of a spatial atomic layer deposition batchprocessor, referred to as a processing chamber 110. The shape of theprocessing chamber 110 and the components described are merely exemplaryand should not be taken as limiting the scope of the disclosure. Forexample the octagonal shaped processing chamber can be circular orhexagonal, etc. A load lock 112 chamber is connected to a front (whichmay be arbitrarily designated as the front) of the processing chamber110 and provides a way of isolating the interior of the processingchamber from the atmosphere outside of the processing chamber 110. Loadlock 112 can be any suitable load lock, and can operate in the manner asany suitable load lock, as is known to those skilled in the art.

A substrate 160 passes into the processing chamber 110 into a loadingregion 120. In the loading region 120, the substrate 160 can besubjected to processing conditions or can rest. Processing conditions inthe loading region can be, for example, pre-heating of the substrate 160to process temperature, exposure to a pre-treatment (e.g., silylamineexposure) or cleaning. In some embodiments, the substrate 160 is exposedto a pre-treatment comprising a gaseous silylamine.

The substrate 160 is moved laterally from the loading region through agas curtain 140 to a first process region 121. The use of ordinalnumbers to describe the process regions is merely exemplary and shouldnot be taken as limiting the scope of the disclosure. Use of the terms“first process region”, “second process region”, etc., are merelyintended as a convenient way of describing different portions of theprocessing chamber. The specific location of the process regions withinthe chamber is not limited to the embodiment shown. Lateral movement ofthe substrate 160 can occur by rotation of a susceptor 166 about an axisindicated by arrow 117, or in the opposite direction of arrow 117. Inthe first process region 121, the substrate 160 may be exposed a firstreactive gas or precursor for an ALD process.

The substrate 160 is moved laterally within the processing chamber 110from the first process region 121 through a gas curtain 140 to a secondprocess region 122. The gas curtains 140 provide separation between thevarious process regions within the processing chamber 110. The gascurtains are shown as a wedge shaped component with a truncated innerend but it will be understood that the gas curtain can be any shapesuitable for maintaining isolation of the process regions. The gascurtain 140 can include any suitable combination of inert gases and/orvacuum ports that are capable of separating the atmospheres of theindividual process regions. In some embodiments, the gas curtains 140comprise, in order, a vacuum port, an inert gas port and another vacuumport. At some point during movement of the substrate from the firstprocess region 121 to the second process region 122, one portion of thesubstrate is exposed to the second process region while another portionof the substrate is exposed to the first process region 121 and a centerportion is within the gas curtain 140.

Once in the second process region 122, the substrate 160 might beexposed to a second reactive gas that can complete the ALD process. Forexample, if a SiN film is being formed, the first reactive gas might bea silicon-containing precursor and the second reactive gas might be anitrogen-containing gas.

The substrate 160 can be continuously laterally moved along the circularpath indicated by arrow 117 to expose the substrate to the third processregion 123, fourth process region 124, fifth process region 125, sixthprocess region 126 and the seventh process region 127 and back to theloading region. In some embodiments, the loading region 120, secondprocess region 122, fourth process region 124 and sixth process region126 each expose the substrate to the second reactive gas comprising analcohol and the first process region 121, third process region 123,fifth process region 125 and seventh process region 127 each expose thesubstrate 160 to the first reactive gas. The embodiment shown in FIG. 2has a wedge shaped gas distribution assembly 130 positioned over thefirst, third, fifth and seventh process regions for clarity to show thesubstrate 160 on the susceptor 166 between gas distribution assemblies130. However, it will be understood that any or all of the processregions can have a gas distribution assembly 130 or other gas deliverysystem.

Once the film 15 has been deposited, further processing may beperformed. For example, de-protection of the first substrate surface 12may occur to remove the silyl-ether terminations. This can be done byany suitable method or technique that can remove the silyl-etherterminations from the surface after depositing the film 15. The furtherprocessing can be performed in the same processing chamber or adifferent processing chamber.

In some embodiments, the silylamine exposure is followed by ALDdeposition cycles. At some intervals, the silyl ether is etched and anew silyl ether layer is formed. In some embodiments, the silyl ether isetched after no more than about 300 ALD cycles, or 200 ALD cycles, or100 ALD cycles, or 75 ALD cycles or 50 ALD cycles. In one or moreembodiments, the etch process is performed after every 100 ALDdeposition cycles, followed by treatment with the silylamine again priorto continuing deposition.

In some embodiments, the process occurs in a batch processing chamber.For example, in a rotating platen chamber, in which one or more wafersare placed on a rotating holder (“platen”). As the platen rotates, thewafers move between various processing areas. For example, in ALD, theprocessing areas would expose the wafer to precursor and reactants. Inaddition, plasma exposure may be useful to properly treat the film orthe surface for enhanced film growth, or to obtain desirable filmproperties.

Some embodiments of the disclosure process a substrate with the firstsurface and the second surface in a single processing chamber where in afirst portion of the chamber, the substrate surfaces are exposed to thesilylamine. The substrate may then be rotated to a second portion of theprocessing chamber, and/or subsequent portion of the processing chamberto deposit a film. In some embodiments, the substrate can be furtherrotated or moved to another portion of the processing chamber where thesilyl ether-terminations can be removed. To separate each or any of theportions, or regions, of the processing chamber, a gas curtain can beemployed. The gas curtain provides one or more of purge gas and vacuumports between the processing regions to prevent reactive gases frommoving from one region to an adjacent region. In some embodiments, thesubstrate is exposed to more than one processing region at the sametime, with one portion of the substrate in a first region (e.g., forsilylamine exposure) and another portion of the substrate at the sametime being in a separate region of the processing chamber.

Embodiments of the disclosure can be used with either a linearprocessing system or a rotational processing system. In a linearprocessing system, the width of the area that the plasma exits thehousing is substantially the same across the entire length of frontface. In a rotational processing system, the housing may be generally“pie-shaped” or “wedge-shaped”. In a wedge-shaped segment, the width ofthe area that the plasma exits the housing changes to conform to a pieshape. As used in this specification and the appended claims, the terms“pie-shaped” and “wedge-shaped” are used interchangeably to describe abody that is a generally circular sector. For example, a wedge-shapedsegment may be a fraction of a circle or disc-shaped object and may havea truncated point. The inner edge of the pie-shaped segment can come toa point or can be truncated to a flat edge or rounded. The path of thesubstrates can be perpendicular to the gas ports. In some embodiments,each of the gas injector assemblies comprises a plurality of elongategas ports which extend in a direction substantially perpendicular to thepath traversed by a substrate. As used in this specification and theappended claims, the term “substantially perpendicular” means that thegeneral direction of movement of the substrates is along a planeapproximately perpendicular (e.g., about 45° to 90°) to the axis of thegas ports. For a wedge-shaped gas port, the axis of the gas port can beconsidered to be a line defined as the mid-point of the width of theport extending along the length of the port.

Additional embodiments of the disclosure are directed to methods ofprocessing a plurality of substrates. The plurality of substrates isloaded onto substrate support in a processing chamber. The substratesupport is rotated to pass each of the plurality of substrates across agas distribution assembly to expose the substrate surface to thesilylamine, deposit a film on the substrate and, optionally, remove thesilyl ether layer.

Rotation of the carousel can be continuous or discontinuous. Incontinuous processing, the wafers are constantly rotating so that theyare exposed to each of the injectors in turn. In discontinuousprocessing, the wafers can be moved to the injector region and stopped,and then to the region between the injectors and stopped. For example,the carousel can rotate so that the wafers move from an inter-injectorregion across the injector (or stop adjacent the injector) and on to thenext inter-injector region where the carousel can pause again. Pausingbetween the injectors may provide time for additional processing betweeneach layer deposition (e.g., exposure to plasma). The frequency of theplasma may be tuned depending on the specific reactive species beingused. Suitable frequencies include, but are not limited to, 400 kHz, 2MHz, 13.56 MHz, 27 MHz, 40 MHz, 60 MHz and 100 MHz.

According to one or more embodiments, the substrate is subjected toprocessing prior to and/or after forming the layer. This processing canbe performed in the same chamber or in one or more separate processingchambers. In some embodiments, the substrate is moved from the firstchamber to a separate, second chamber for further processing. Thesubstrate can be moved directly from the first chamber to the separateprocessing chamber, or the substrate can be moved from the first chamberto one or more transfer chambers, and then moved to the separateprocessing chamber. Accordingly, the processing apparatus may comprisemultiple chambers in communication with a transfer station. An apparatusof this sort may be referred to as a “cluster tool” or “clusteredsystem”, and the like.

Generally, a cluster tool is a modular system comprising multiplechambers which perform various functions including substratecenter-finding and orientation, degassing, annealing, deposition and/oretching. According to one or more embodiments, a cluster tool includesat least a first chamber and a central transfer chamber. The centraltransfer chamber may house a robot that can shuttle substrates betweenand among processing chambers and load lock chambers. The transferchamber is typically maintained at a vacuum condition and provides anintermediate stage for shuttling substrates from one chamber to anotherand/or to a load lock chamber positioned at a front end of the clustertool. Two well-known cluster tools which may be adapted for the presentdisclosure are the Centura® and the Endura®, both available from AppliedMaterials, Inc., of Santa Clara, Calif. The details of one suchstaged-vacuum substrate processing apparatus are disclosed in U.S. Pat.No. 5,186,718, entitled “Staged-Vacuum Wafer Processing Apparatus andMethod,” Tepman et al., issued on Feb. 16, 1993. However, the exactarrangement and combination of chambers may be altered for purposes ofperforming specific steps of a process as described herein. Otherprocessing chambers which may be used include, but are not limited to,cyclical layer deposition (CLD), atomic layer deposition (ALD), chemicalvapor deposition (CVD), physical vapor deposition (PVD), etch,pre-clean, chemical clean, thermal treatment such as RTP, plasmanitridation, degas, orientation, hydroxylation and other substrateprocesses. By carrying out processes in a chamber on a cluster tool,surface contamination of the substrate with atmospheric impurities canbe avoided without oxidation prior to depositing a subsequent film.

According to one or more embodiments, the substrate is continuouslyunder vacuum or “load lock” conditions, and is not exposed to ambientair when being moved from one chamber to the next. The transfer chambersare thus under vacuum and are “pumped down” under vacuum pressure. Inertgases may be present in the processing chambers or the transferchambers. In some embodiments, an inert gas is used as a purge gas toremove some or all of the reactants after forming the layer on thesurface of the substrate. According to one or more embodiments, a purgegas is injected at the exit of the deposition chamber to preventreactants from moving from the deposition chamber to the transferchamber and/or additional processing chamber. Thus, the flow of inertgas forms a curtain at the exit of the chamber.

During processing, the substrate can be heated or cooled. Such heatingor cooling can be accomplished by any suitable means including, but notlimited to, changing the temperature of the substrate support (e.g.,susceptor) and flowing heated or cooled gases to the substrate surface.In some embodiments, the substrate support includes a heater/coolerwhich can be controlled to change the substrate temperatureconductively. In one or more embodiments, the gases (either reactivegases or inert gases) being employed are heated or cooled to locallychange the substrate temperature. In some embodiments, a heater/cooleris positioned within the chamber adjacent the substrate surface toconvectively change the substrate temperature.

The substrate can also be stationary or rotated during processing. Arotating substrate can be rotated continuously or in discreet steps. Forexample, a substrate may be rotated throughout the entire process, orthe substrate can be rotated by a small amount between exposures todifferent reactive or purge gases. Rotating the substrate duringprocessing (either continuously or in steps) may help produce a moreuniform deposition or etch by minimizing the effect of, for example,local variability in gas flow geometries.

Trimethylsilylamide Preparation

One way to prepare the tirmethylsilylamide compound is by saltmetathesis by treating lithium amide with trimethylsilylchloride. Thereaction scheme is shown in Equation 1,

where L can be equal to any amine or heterocyclic amine. Some specificexamples of amines are dimethylamine, diethylamine, pyrollidine,pyrazole and pyrrole.

Synthesis of 1-trimethylsilylpyrrolidine

Equation 2 shows the synthetic scheme for 1-trimethylsilylpyrrolidine,referred to as BL1. 6.5 mL (80 mmol) of pyrrolidine was dissolved in 250mL hexane and the solution was cooled down to −78° C. To this solution,50 mL (80 mmol) of 1.6 M n-butyl lithium in hexane was added drop wiseover a period of 15 min. The resultant reaction mixture was allowed toreach room temperature slowly and stirred for 30 min. The reactionmixture was then again cooled to −78° C. and a 20 mL hexane solutioncontaining 10.1 mL (80 mmol) trimethylsilyl chloride was added over aperiod of 10 min. The reaction mixture was allowed to reach roomtemperature slowly and stirred for 12 h. The white precipitate wasfiltered under an inert atmosphere and hexane was evaporated undervacuum. The product was distilled as a colorless liquid at 110° C. @ 760torr. Yield: 8.9 g (77.5%). ¹HNMR (400.18 MHz, C₆D₆) 2.87 (m, 4H), 1.57(m, 4H), 0.11 (s, 9H) ppm; ¹³CNMR (100.64 MHz, C₆D₆) 1.08 ppm.

Synthesis of 1-trimethylsilylpyrrole

Equation 3 shows a synthetic scheme for 1-trimethylsilylpyrrole, alsoreferred to as BL2. First, 5.55 mL (80 mmol) of pyrrole was dissolved in250 mL hexane and the solution was cooled down to −78° C. To thesolution, 50 mL (80 mmol) of 1.6 M n-butyl lithium in hexane was addeddrop wise over a period of 15 min. The resultant reaction mixture wasallowed to attain room temperature slowly and stirred for 30 min. Thereaction mixture was then again cooled to −78° C. and a 20 mL hexanesolution of 10.1 mL (80 mmol) trimethylsilyl chloride was added over aperiod of 10 min. The reaction mixture was allowed to attain roomtemperature slowly and stirred for 12 h. The white precipitate wasfiltered under inert atmosphere and hexane was evaporated under vacuum.The product was distilled as a colorless liquid at 130° C. @ 760 torr.Yield: 8.7 g (78.2%). ¹HNMR (400.18 MHz, C₆D₆) 6.74 (s, 2H), 6.54 (s,2H), 0.07 (s, 9H) ppm; ¹³CNMR (100.64 MHz, C₆D₆) 123.47, 112.20, −0.01ppm. Mass spectrometry: m/Z calc for [M+H]⁺=140.1, found 140.2.

Synthesis of 3,5-dimethyl-1-trimethylsilylpyrazole

Equation 4 shows a synthetic scheme for3,5-dimethyl-1-trimethylsilylpyrazole, also referred to as BL3. 7.7 g(80 mmol) of 3,5-dimethyl pyrazole was dissolved in 250 mL hexane andthe solution was cooled down to −78° C. To this solution, 50 mL (80mmol) of 1.6 M n-butyl lithium in hexane was added drop wise over aperiod of 15 min. Resultant reaction mixture was allowed to attain roomtemperature slowly and stirred for 30 min. The reaction mixture was thenagain cooled to −78° C. and a 20 mL hexane solution of 10.1 mL (80 mmol)trimethylsilyl chloride was added over a period of 10 min. Reactionmixture was allowed to attain room temperature slowly and stirred for 12h. White precipitate was filtered under inert atmosphere and hexane wasevaporated under vacuum. Product was distilled as a colorless liquid at70° C. @ 20 torr. Yield: 9.4 g (70.0%). ¹HNMR (400.18 MHz, C₆D₆) 5.80(S, 1H), 2.30 (S, 3H), 2.00 (s, 3H), 0.32 (s, 9H) ppm; ¹³CNMR (100.64MHz, C₆D₆) 151.97, 146.04, 108.40, 32.54, 23.63, 1.02 ppm.

The synthetic preparation, characterization, and properties, accordingto ¹HNMR and ¹³CNMR demonstrated good purity and high yields. Accordingto the TGA analysis, these molecules were volatile (highest evaporationrate was between 90-137° C.) and thermally stable with residues of ˜0%.

EXAMPLES

Trimethylsilylamides were tested as blocking layers by treatingsubstrates (Si(H), SiO₂ 1K, Si(native oxide)) in vapor phase with BL1 at350° C. ALD of SiN at the same temperature was then performed. Thesilicon precursor used was silicon tetrabromide and thenitrogen-containing precursor comprised ammonia (30 T). There were atotal of 100 cycles. Table 1 shows the results from a 2.4 Torr soak ofdiffering lengths with BL1. Table 2 shows the results of a 5 Torr soakfor 30 seconds.

TABLE 1 Soak Time Film Thickness (Å) (min) Si(H) Si(native O) SiO₂ 1K 3030.4 4.58 2.65 10 28.4 2.02 2.18 5 31.7 4.98 2.12 1 32.5 5.2 2.59 0.531.33 7.19 2.62 0 28.5 28.23 20.39

TABLE 2 Soak Time Film Thickness (Å) (min) Si(H) Si(native O) SiO₂ 1K0.5 25.3 1.1 0.84

When BL1 was not used as a pretreatment, there was very little observedselectivity with respect to Si(H), SiO₂ 1K and Si(native O). BL1 Soaktimes of greater than 1 minute at 2 T enabled very good selectivity.According to contact angle measurements, there was little or no SiNdeposited on the SiO₂ and Si(native O) substrates. This was verified bythe hydrophillicity on Si(H) vs. hydrophobicity on SiO₂ and Si(nativeO). At 30 seconds of BL1 soak time, there was still some selectivitybased on Ellipsometry, however, the contact angles were very similar,which might suggest that there is SiN on all three surfaces. Increasingthe pressure to 5 T for 30 seconds recovered the selectivity.

The selectivity of BL1 as a function of the number of cycles was alsoevaluated. The results are collected in Table 3. After 100 cycles, aselectivity of ˜8.6 (Si(H) vs SiO₂) was observed. After 100 cycles theselectivity appeared to decrease. Without being bound by any particulartheory of operation, it is believed that the BL1 blocking layer promotesa nucleation delay which lasts about 100 cycles.

TABLE 3 Number of ALD Film Thickness (Å) cycles Si(H) Si(native O) SiO₂1K 50 13 1 1 100 29 5 3 150 47 25 17 200 111 86 82

While the foregoing is directed to embodiments of the presentdisclosure, other and further embodiments of the disclosure may bedevised without departing from the basic scope thereof, and the scopethereof is determined by the claims that follow.

What is claimed is:
 1. A method of depositing a film, the methodcomprising: providing a substrate comprising a first substrate surfaceincluding a hydroxyl-terminated surface and a second substrate surfaceincluding a hydrogen-terminated surface; exposing the substrate to asilylamide to react with the hydroxyl-terminated surface to form a silylether-terminated surface; and exposing the substrate to one or moredeposition gases to deposit a film on the second substrate surfaceselectively over the silyl ether-terminated surface.
 2. The method ofclaim 1, wherein the silylamide comprises an organic silylamide.
 3. Themethod of claim 2, wherein the organic silylamide comprises a siliconatom bonded to substantially only to carbon and/or nitrogen atoms. 4.The method of claim 2, wherein the organic silylamide comprisessubstantially no Si—H or Si—OH bonds.
 5. The method of claim 2, whereinthe organic silylamide comprises one or more of trimethylsilylamide,triethylsilylamide, ethyldimethylsilylamide and/ordiethylmethylsilylamide.
 6. The method of claim 1, wherein thesilylamide includes an amide comprising one or more of pyrrolidine,pyrrole, pyrazole, dimethylamine, diethylamine, ethylmethylamine, cyclicsecondary amine, saturated cyclic amine and/or unsaturated cyclic amine.7. The method of claim 1, wherein the silylamide comprises one or moreof 1-trimethylsilylpyrrolidine, 1-trimethylsilylpyrrole and/or3,5-dimethyl-1-trimethylsilylpyrazole.
 8. The method of claim 1, whereinone or more of the first substrate surface and the second substratesurface comprises a dielectric.
 9. The method of claim 8, wherein thefirst substrate surface comprises a dielectric.
 10. The method of claim1, further comprising etching the silyl ether-terminated surface after apredetermined amount of film is deposited followed by re-exposure to thesilylamine to re-form the silyl ether-terminated surface and additionalfilm deposition.
 11. The method of claim 10, wherein the silylether-terminated surface is etched and re-formed after no more than 100ALD cycles of deposition.
 12. The method of claim 1, wherein thesubstrate is exposed to the silylamide for a time in the range of about10 seconds to about 60 minutes.
 13. The method of claim 1, wherein thefilm comprises SiN.
 14. The method of claim 13, wherein the film isdeposited by atomic layer deposition comprising sequential exposure to asilicon-containing gas and a nitrogen-containing gas.
 15. The method ofclaim 14, wherein the silicon containing gas comprises one or more ofsilane, disilane, trisilane, monochlorosilane, dichlorosilane,trichlorosilane, silicon tetrachloride, hexachlorodisilane (HCDS), ahalogenated carbosilane.
 16. The method of claim 14, wherein thenitrogen-containing gas comprises one or more of a nitrogen-containingplasma, ammonia, an amine, hydrazine and/or carbonitride.
 17. A methodof depositing a film, the method comprising: providing a substratecomprising a first substrate surface including a hydroxyl-terminatedsurface and a second substrate surface including a hydrogen-terminateddielectric; soaking the substrate with a silylamide to react with thehydroxyl-terminated surface to form a silyl ether-terminated surface;and exposing to the substrate to one or more deposition gases to deposita silicon nitride film on the second substrate surface selectively overthe first substrate surface.
 18. The method of claim 17, wherein thesilylamide comprises silicon atoms bonded to substantially only tocarbon and/or nitrogen atoms and there are substantially no Si—H orSi—OH bonds, and the silylamide includes an amide comprising one or moreof pyrrolidine, pyrrole, pyrazole, dimethylamine, diethylamine,ethylmethylamine, cyclic secondary amine, saturated cyclic amine and/orunsaturated cyclic amine.
 19. The method of claim 18, wherein thesilylamide comprises one or more of 1-trimethylsilylpyrrolidine,1-trimethylsilylpyrrole and/or 3,5-dimethyl-1-trimethylsilylpyrazole.20. A method of depositing a film, the method comprising: providing asubstrate comprising a first substrate surface including ahydroxyl-terminated surface and a second substrate surface including ahydrogen-terminated dielectric; soaking the substrate with a silylamidecomprising one or more of 1-trimethylsilylpyrrolidine,1-trimethylsilylpyrrole and/or 3,5-dimethyl-1-trimethylsilylpyrazole toreact with the hydroxyl-terminated surface to form a silylether-terminated surface; and exposing to the substrate to one or moredeposition gases to deposit a silicon nitride film on the secondsubstrate surface selectively over the first substrate surface.